The present invention relates to novel hetaroyl derivatives of the formula I 
where:
R1 and R2 are each hydrogen, nitro, halogen, cyano, thiocyanato, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C2-C6-alkenylthio, C2-C6-alkynylthio, C1-C6-alkylsulfinyl, Cl-C6-haloalkylsulfinyl, C2-C6-alkenylsulfinyl, C2-C6-alkynylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, C1-C6-alkoxysulfonyl, C1-C6-haloalkoxysulfonyl, C2-C6-alkenyloxysulfonyl, C2-C6-alkynyloxysulfonyl, phenyl, phenyloxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups:
nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy;
Z is a building block from the group consisting of Z1 to Z12. 
xe2x80x83where
R3, R5, R7 and R9 are each hydrogen, halogen, C1-C-4-alkyl, C1-C-4-haloalkyl, C1-C-4-alkoxy, C1-C-4-haloalkoxy, C1-C-4-alkylthio, C1-C-4-haloalkythio, nitro, cyano, hydroxyl, mercapto, C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C2-C4-alkenylthio, C2-C4-alkynylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C2-C4-alkenylsulfinyl, C2-C4-alkynylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, C2-C4-alkenylsulfonyl, C2-C4-alkynylsulfonyl C1-C4-alkoxysulfonyl, C1-C4-haloalkoxysulfonyl, C2-C4-alkenyloxysulfonyl, C2-C4alkynyloxysulfonyl, xe2x80x94NR12R13, xe2x80x94CO2R12, xe2x80x94CONR12R13, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups:
nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy;
R4, R6, R8 and R10 are each hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio or C1-C4-haloalkylthio;
or a xe2x80x94CR3R4xe2x80x94, xe2x80x94CR5R6xe2x80x94, xe2x80x94CR7R8xe2x80x94 or xe2x80x94CR9R10xe2x80x94 unit may be replaced by Cxe2x95x90O or Cxe2x95x90NR13;
R11 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylcarbonyl, C1-C6-haloalkylcarbonyl, xe2x80x94CO2R12, xe2x80x94CONR12R13 or SO2R12;
R12 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-alkenyl, C3-C6-alkynyl or phenyl, where the last radical may be partially or fully halogenated and may carry one to three of the following radicals:
nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy;
R13 is C1-C6-alkoxy, C1-C6-haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy or one of the radicals mentioned under R12;
Q is an unsubstituted or substituted cyclohexane-1,3-dione ring linked through position 2;
and their agriculturally useful salts.
The invention additionally relates to processes for preparing compounds of the formula I, to compositions comprising compounds of the formula I and to the use of these derivatives or to compositions comprising these derivatives for controlling harmful plants.
2-Hetaroylcyclohexanediones are known from the literature, for example from EP-A 283 261.
However, the herbicidal properties of these prior art compounds and their compatibility with crop plants are not entirely satisfactory. It is therefore an object of the present invention to provide novel, in particular herbicidally active, compounds with improved properties.
We have found that this object is achieved by the hetaroyl derivatives of the formula I and their herbicidal action.
Furthermore, the invention provides herbicidal compositions comprising the compounds I and having a very good herbicidal activity. Additionally, the invention provides processes for preparing these compositions and methods for controlling undesirable plant growth using the compounds I.
Depending on the substitution pattern, the compounds of the formula I may contain one or more chiral centers and, if this is the case, be present as enantiomers or as mixtures of diastereomer. The invention provides the pure enantiomers or diastereomers and mixtures thereof.
The compounds of the formula I may also be present in the form of their agriculturally useful salts, the kind of salt generally not being important. The salts of those cations or the acid addition salts of those acids whose cations or anions, respectively, do not adversely affect the herbicidal activity of the compounds I are generally suitable.
Suitable cations are in particular ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and ammonium which may, if desired, carry one to four C1-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropyl-ammonium, tetramethylammonium, tetrabutylammonium, trimethyl-benzylammonium, and further phosphonium ions and sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
Particular preference is given to the compounds of the formula I according to the invention where the variable Q is a cyclohexane-1,3-dione ring, linked through position 2, of the formula II 
where II also represents the tautomeric forms IIxe2x80x2 and IIxe2x80x3
where
R14, R15, R17 and R19 are each hydrogen or C1-C4-alkyl;
R16 is hydrogen, C1-C4-alkyl or C3-C4-cycloalkyl, where the last two groups may carry one to three of the following substituents:
halogen, C1-C4-alkylthio or C1-C4-alkoxy; or
is tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-3-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl or 1,3-dithian-2-yl, where the last 6 radicals may be substituted by one to three C1-C4-alkyl radicals;
R18 is hydrogen, C1-C4-alkyl or C1-C6-alkoxycarbonyl; or
R16 and R19 together form a bond or a three- to six-membered carbocyclic ring; or
the xe2x80x94CR16R17xe2x80x94 unit may be replaced by Cxe2x95x90O.
The organic moieties mentioned for the substituents R1-R19 or as radicals on phenyl rings represent collective terms for lists of the individual group members. All hydrocarbon chains, ie. all the alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkoxysulfonyl, haloalkoxysulfonyl, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, alkenyl, alkenyloxy, alkenylthio, alkenylsulfinyl, alkenylsulfonyl, alkenyloxysulfonyl, alkynyl, alkynyloxy, alkynylthio, alkynylsulfinyl, alkynylsulfonyl and alkynyloxysulfonyl moieties, may be straight-chain or branched. Unless stated otherwise, preference is given to halogenated substituents carrying one to five identical or different halogens. Halogen is in each case fluorine, chlorine, bromine or iodine.
Furthermore, the following moieties represent, for example:
C1-C4-alkyl and the alkyl moieties of C1-C4-alkylcarbonyl: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
C1-C6-alkyl and the alkyl moieties of C1-C6-alkylcarbonyl: C1-C4-alkyl as mentioned above, and pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-3-methylpropyl;
C1-C4-haloalkyl and the haloalkyl moieties of C1-C4-haloalkylcarbonyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;
C1-C6-haloalkyl and the haloalkyl moieties of C1-C6-haloalkylcarbonyl: C1-C4-haloalkyl as mentioned above, and 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;
C1-C4-alkoxy and the alkoxy moieties in C1-C4-alkoxycarbonyl; methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy;
C1-C6-alkoxy and the alkoxy moieties in C1-C6-alkoxycarbonyl: C1-C4-alkoxy as mentioned above, and pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,l-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy;
C1-C4-haloalkoxy: a C1-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy;
C1-C6-haloalkoxy: C1-C4-haloalkoxy as mentioned above, and 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy and dodecafluorohexoxy;
C1-C4-alkylthio: methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,l-dimethylethylthio;
C1-C6-alkylthio: C1-C4-alkylthio as mentioned above, and pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1-ethyl-2-methylpropylthio;
C1-C4-haloalkylthio: a C1-C4-alkylthio radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2,3-dichloropropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio and nonafluorobutylthio;
C1-C6-haloalkylthio: C1-C4-haloalkylthio as mentioned above, and 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio and dodecafluorohexylthio;
C1-C4-alkylsulfinyl (C1-C4-alkyl-S(xe2x95x90O)xe2x80x94): methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1,1-dimethylethylsulfinyl;
C1-C6-alkylsulfinyl: C1-C4-alkylsulfinyl as mentioned above, and pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl and 1-ethyl-2-methylpropylsulfinyl;
C1-C4-haloalkylsulfinyl: a C1-C4-alkylsulfinyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl, 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2,2-difluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 2,2,2-trichloroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2-chloro-2,2-difluoroethylsulfinyl, 2,2-dichloro-2-fluoroethylsulfinyl, pentafluoroethylsulfinyl, 2-fluoropropylsulfinyl, 3-fluoropropylsulfinyl, 2-chloropropylsulfinyl, 3-chloropropylsulfinyl, 2-bromopropylsulfinyl, 3-bromopropylsulfinyl, 2,2-difluoropropylsulfinyl, 2,3-difluoropropylsulfinyl, 2,3-dichloropropylsulfinyl, 3,3,3-trifluoropropylsulfinyl, 3,3,3-trichloropropylsulfinyl, 2,2,3,3,3-pentafluoropropylsulfinyl, heptafluoropropylsulfinyl, 1-(fluoromethyl)-2-fluoroethylsulfinyl, 1-(chloromethyl)-2-chloroethylsulfinyl, 1-(bromomethyl)-2-bromoethylsulfinyl, 4-fluorobutylsulfinyl, 4-chlorobutylsulfinyl, 4-bromobutylsulfinyl and nonafluorobutylsulfinyl;
C1-C6-haloalkylsulfinyl: C1-C4-haloalkylsulfinyl as mentioned above, and 5-fluoropentylsulfinyl, 5-chloropentylsulfinyl, 5-bromopentylsulfinyl, 5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl and dodecafluorohexylsulfinyl;
C1-C4-alkylsulfonyl (C1-C4-alkyl-S(xe2x95x90O)2xe2x80x94): methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1,1-dimethylethylsulfonyl;
C1-C6-alkylsulfonyl: C1-C4-alkylsulfonyl as mentioned above, and pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl and 1-ethyl-2-methylpropylsulfonyl;
C1-C4-haloalkylsulfonyl: a C1-C4-alkylsulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2,3-dichloropropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl, 1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(choromethyl)-2-chloroethylsulfonyl, 1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl and nonafluorobutylsulfonyl;
C1-C6-haloalkylsulfonyl: C1-C4-haloalkylsulfonyl as mentioned above, and 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorohexylsulfonyl, 6-bromohexylsulfonyl, 6-iodohexylsulfonyl and dodecafluorohexylsulfonyl;
C1-C4-alkoxysulfonyl: methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, 1-methylethoxysulfonyl, butoxysulfonyl, 1-methylpropoxysulfonyl, 2-methylpropoxysulfonyl and 1,1-dimethylethoxysulfonyl;
C1-C6-alkoxysulfonyl: C1-C4-alkoxysulfonyl as mentioned above, and pentoxysulfonyl, 1-methylbutoxysulfonyl, 2-methylbutoxysulfonyl, 3-methylbutoxysulfonyl, 1,1-dimethylpropoxysulfonyl, 1,2-dimethylpropoxysulfonyl, 2,2-dimethylpropoxysulfonyl, 1-ethylpropoxysulfonyl, hexoxysulfonyl, 1-methylpentoxysulfonyl, 2-methylpentoxysulfonyl, 3-methylpentoxysulfonyl, 4-methylpentoxysulfonyl, 1,1-dimethylbutoxysulfonyl, 1,2-dimethylbutoxysulfonyl, 1,3-dimethylbutoxysulfonyl, 2,2-dimethylbutoxysulfonyl, 2,3-dimethylbutoxysulfonyl, 3,3-dimethylbutoxysulfonyl, 1-ethylbutoxysulfonyl, 2-ethylbutoxysulfonyl, 1,1,2-trimethylpropoxysulfonyl, 1,2,2-trimethylpropoxysulfonyl, 1-ethyl-1-methylpropoxysulfonyl and 1-ethyl-2-methylpropoxysulfonyl;
C1-C4-haloalkoxysulfonyl: a C1-C4-alkoxysulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, ie. for example fluoromethoxysulfonyl, difluoromethoxysulfonyl, trifluoromethoxysulfonyl, chlorodifluoromethoxysulfonyl, bromodifluoromethoxysulfonyl, 2-fluoroethoxysulfonyl, 2-chloroethoxysulfonyl, 2-bromoethoxysulfonyl, 2-iodoethoxysulfonyl, 2,2-difluoroethoxysulfonyl, 2,2,2-trifluoroethoxysulfonyl, 2-chloro-2-fluoroethoxysulfonyl, 2-chloro-2,2-difluoroethoxysulfonyl, 2,2-dichloro-2-fluoroethoxysulfonyl, 2,2,2-trichloroethoxysulfonyl, pentafluoroethoxysulfonyl, 2-fluoropropoxysulfonyl, 3-fluoropropoxysulfonyl, 2-chloropropoxysulfonyl, 3-chloropropoxysulfonyl, 2-bromopropoxysulfonyl, 3-bromopropoxysulfonyl, 2,2-difluoropropoxysulfonyl, 2,3-difluoropropoxysulfonyl, 2,3-dichloropropoxysulfonyl, 3,3,3-trifluoropropoxysulfonyl, 3,3,3-trichloropropoxysulfonyl, 2,2,3,3,3-pentafluoropropoxysulfonyl, heptafluoropropoxysulfonyl, 1-(fluoromethyl)-2-fluoroethoxysulfonyl, 1-(chloromethyl)-2-chloroethoxysulfonyl, 1-(bromomethyl)-2-bromoethoxysulfonyl, 4-fluorobutoxysulfonyl, 4-chlorobutoxysulfonyl, 4-bromobutoxysulfonyl and 4-iodobutoxysulfonyl;
C1-C6-haloalkoxysulfonyl: C1-C4-haloalkoxysulfonyl as mentioned above, and 5-fluoropentoxysulfonyl, 5-chloropentoxysulfonyl, 5-bromopentoxysulfonyl, 5-iodopentoxysulfonyl, undecafluoropentoxysulfonyl, 6-fluorohexoxysulfonyl, 6-chlorohexoxysulfonyl, 6-bromohexoxysulfonyl, 6-iodohexoxysulfonyl and dodecafluorohexoxysulfonyl;
C2-C4-alkenyl, and the alkenyl moieties of C2-C4-alkenyloxy, C2-C4-alkenylthio, C2-C4-alkenylsulfinyl, C2-C4-alkenylsulfonyl and C2-C4-alkenyloxysulfonyl: ethenyl, prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1-methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl and 2-methylprop-2-en-1-yl;
C2-C6-alkenyl, and the alkenyl moieties of C2-C6-alkenyloxy, C2-C6-alkenylthio, C2-C6-alkenylsulfinyl, C2-C6-alkenylsulfonyl and C2-C6-alkenyloxysulfonyl: C2-C4-alkenyl as mentioned above, and penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3,3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl;
C2-C4-alkynyl and the alkynyl radicals of C2-C4-alkynyloxy, C2-C4-alkynylthio, C2-C4-alkynylsulfinyl, C2-C4-alkynylsulfonyl and C2-C4-alkynyloxysulfonyl: ethynyl, prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn-1-yl, but-1-yn-3-yl, but-1-yn-4-yl and but-2-yn-1-yl;
C2-C6-alkynyl, and the alkynyl radicals of C2-C6-alkynyloxy, C2-C6-alkynylthio, C2-C6-alkynylsulfinyl, C2-C6-alkynylsulfonyl and C2-C6-alkynyloxysulfonyl: C2-C4-alkynyl as mentioned above, and pent-1-yn-1-yl, pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl, pent-2-yn-1-yl, pent-2-yn-4-yl, pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-1-yl, hex-1-yn-3-yl, hex-1-yn-4-yl, hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl, hex-2-yn-4-yl, hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl, hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl and 4-methylpent-2-yn-5-yl;
C3-C4-cycloalkyl: cyclopropyl and cyclobutyl.
All phenyl rings are preferably unsubstituted or carry one to three halogens and/or a nitro group, a cyano radical, or a methyl, trifluoromethyl, methoxy or trifluoromethoxy substituent.
With respect to the use of the compounds of the formula I according to the invention as herbicides, the variables preferably have the meanings below, in each case on their own or in combination:
R1 is nitro, halogen, cyano, thiocyanato, hydroxyl, mercapto, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C2-C6-alkenylthio, C2-C6-alkynylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C2-C6-alkenylsulfinyl, C2-C6-alkynylsulfinyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, C1-C6-alkoxysulfonyl, C1-C6-haloalkoxysulfonyl, C2-C6-alkenyloxysulfonyl, C2-C6-alkynyloxysulfonyl, phenyl, phenyloxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups:
nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-c4-haloalkoxy;
particularly preferably nitro, halogen, hydroxyl, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl or phenyl, where the last radical is unsubstituted or may carry one to three halogens and/or a nitro group, a cyano radical, or a methyl, trifluoromethyl, methoxy or trifluoromethoxy substituent;
especially preferably nitro, fluorine, chlorine, bromine, hydroxyl, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylsulfonyl, ethylsulfonyl, trifluoromethylsulfonyl, pentafluoroethylsulfonyl or phenyl;
R2 is hydrogen, halogen or C1-C6-alkyl; particularly preferably hydrogen, chlorine, bromine or methyl;
Z is Z1, Z2, Z3, Z4, Z5, Z6, Z7, Z8, Z9, Z10, Z11or Z12;
R3, R5, R7 and R9 are each hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, nitro, cyano, hydroxyl, mercapto,
C2-C4-alkenyl, C2-C4-alkynyl, C2-C4-alkenyloxy, C2-C4-alkynyloxy, C2-C4-alkenylthio, C2-C4-alkynylthio, C1-C4-alkylsulfinyl, C1-C4-haloalkylsulfinyl, C2-C4-alkenylsulfinyl, C2-C4-alkynylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, C2-C4-alkenylsulfinyl, C2-C4-alkynylsulfonyl, C1-C4-alkoxysulfonyl, C1-C4-haloalkoxysulfonyl, C2-C4-alkenyloxysulfonyl, C2-C4-alkynyloxysulfinyl, xe2x80x94NR12R13, xe2x80x94CO2R12, xe2x80x94CONR12R13, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, where the last five substituents may be partially or fully halogenated and may carry one to three of the following groups:
nitro, cyano, hydroxyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy;
particularly preferably hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, nitro, cyano, hydroxyl, C1-C6-alkoxycarbonyl or phenyl, where the last radical is unsubstituted or may carry one to three halogens and/or a nitro group, a cyano radical, or a methyl, trifluoromethyl, methoxy or trifluoromethoxy substituent;
especially preferably hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, difluoromethoxy, nitro, cyano, hydroxyl, methoxycarbonyl, ethoxycarbonyl or phenyl;
R4, R6, R8 and R10 are each hydrogen, halogen or C1-C4-alkyl; particularly preferably hydrogen, fluorine, chlorine, methyl or ethyl; especially preferably hydrogen;
R11 is hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkylcarbonyl, C1-C6-haloalkylcarbonyl, C1-C6-alkylsulfonyl, C1-C6-haloalkylsulfonyl or phenylsulfonyl, where the last phenyl radical may be substituted by a C1-C4-alkyl radical; particularly preferably methyl, ethyl, difluoromethyl, trifluoromethyl, methylcarbonyl, ethylcarbonyl, isopropylcarbonyl, trifluoromethylcarbonyl, methylsulfonyl, trifluoromethylsulfonyl, phenylsulfonyl or 4-methylphenylsulfonyl;
R12 is hydrogen or C1-C6-alkyl; particularly preferably hydrogen, methyl or ethyl;
R13 is hydrogen, C1-C6-alkyl, C1-C6-alkoxy, C3-C6-alkenyloxy or C3-C6-alkynyloxy; particularly preferably methyl, ethyl, methoxy, ethoxy, 2-propen-1-yloxy, 2-propyn-1-yloxy or 1-methyl-2-propyn-1-yloxy;
R14, R15, R17 and R19 are each hydrogen or C1-C4-alkyl; particularly preferably hydrogen, methyl or ethyl;
R16 is hydrogen, C1-C4-alkyl or C3-C4-cycloalkyl, where the last two groups may carry one to three of the following substituents: halogen, C1-C4-alkoxy or C1-C4-alkylthio; tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-3-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithian-2-yl or 1,3-dithiolan-2-yl, where the last six groups may be unsubstituted or may carry up to three C1-C4-alkyl radicals; particularly preferably hydrogen, methyl, ethyl, cyclopropyl, di(methoxy)methyl, di(ethoxy)methyl, 2-ethylthiopropyl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1,3-dioxolan-2-yl, 1,3-dioxan-2-yl, 5,5-dimethyl-1-3-dioxan-2-yl [sic], 1,3-oxathiolan-2-yl, 1,3-oxathian-2-yl, 1,3-dithiolan-2-yl, 5,5-dimethyl-1,3-dithian-2-yl or 1-methylthiocyclopropyl;
R18 is hydrogen, C1-C4-alkyl or C1-C4-alkoxycarbonyl; particularly preferably hydrogen, methyl or methoxycarbonyl.
It is also possible for R16 and R19 to form a xcfx80 bond, thus giving rise to a double bond system.
If desired, the xe2x80x94CR16R17xe2x80x94 unit may be replaced by Cxe2x95x90O.
Preference is given to compounds of the formula I wherein the variable Z is Z1, Z2, Z11 or Z12.
Preference is also given to the compounds of the formula I wherein the variable Z is Z3, Z4, Z5, Z6, Z7 or Z8.
Preference is also given to the compounds of the formula I wherein the variable Z is Z9 or Z10.
Particular preference is given to compounds of the formulae Ia-Ic (Z=Z1) and Id-Ie (Z=Z2) and their N-oxides Iaxe2x80x2-Icxe2x80x2 (Z=Z11) and Idxe2x80x2-Iexe2x80x2 (Z=Z12) and particular preference is also given to compounds of the formulae If (Z=Z9) and Ig (Z=Z10). 
Furthermore, preference is given to the compounds Ia, Ib, Ic, Id and Ie.
Preference is also given to the compounds If and Ig where CR3R4, CR5R6, CR7R8 and/or CR9R10 may not be replaced by Cxe2x95x90O or Cxe2x95x90NR13.
Furthermore, preference is given to the compounds Ig where CR5R6 is replaced by Cxe2x95x90O or Cxe2x95x90NR13.
Furthermore, preference is given to the compounds Ig where CR3R4, CR7R8 and/or CR8R10 [sic] are replaced by Cxe2x95x90O or Cxe2x95x90NR13.
Very particular preference is given to the compounds Ia1 ({circumflex over (=)}I where R2, R14, R15, R16, R17, R18 and R19=H and where the xe2x80x9cQxe2x80x94COxe2x80x94fragmentxe2x80x9d is attached in position a, R1 is attached in position d and Z1 is attached in positions b and c) listed in Table 1.
Furthermore, very particular preference is given to the following hetaroyl derivatives of the formula I:
the compounds Ia2.001-Ia2.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R16 is methyl: 
the compounds Ia3.001-Ia3.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R16 and R17 are each methyl: 
the compounds Ia4.001-Ia4.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R18 and R19 are each methyl: 
the compounds Ia5.001-Ia5.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
the compounds Ia6.001-Ia6.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R14, R18 and R19 are each methyl and in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
the compounds Ia7.001-Ia7.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R141 R15, R18 and R19 are each methyl and in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
the compounds Iaxe2x80x21.001-Iaxe2x80x2.1.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that they are the N-oxides (Z=Z11): 
the compounds Iaxe2x80x22.001-Iaxe2x80x22.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R16 is methyl and in that they are the N-oxides (Z=Z11) 
the compounds Iaxe2x80x23.001-Iaxe2x80x23.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R16 and R17 are each methyl and in that they are the N-oxides (Z=Z11): 
the compounds Iaxe2x80x24.001-Iaxe2x80x24.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R18 and R19 are each methyl and in that they are the N-oxides (Z=Z11): 
the compounds Ia,5.001-Iaxe2x80x25.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O and in that they are the N-oxides (Z=Z11): 
the compounds Iaxe2x80x26.001-Iaxe2x80x26.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R14, R18 and R19 are each methyl, the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O and in that they are the N-oxides (Z=Z11): 
the compounds Iaxe2x80x27.001-Iaxe2x80x27.211, which differ from the corresponding compounds Ia1.001-Ia1.211 in that R14, R15, R18 and R19 are each methyl, the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O and in that they are the N-oxides (Z=Z11): 
Likewise, very particular preference is given to the compounds Ib1 ({circumflex over (=)}I where R14, R15, R16, R17, R18 and R19 =H and where the xe2x80x9cQxe2x80x94COxe2x80x94 fragmentxe2x80x9d is attached in position e, R1 is attached in position d, R2 is attached in position a and Z1 is attached in positions b and c) listed in Table 2 below.
Furthermore, very particular preference is given to the following hetaroyl derivatives of the formula I:
the compounds Ib2.01-Ib2.21, which differ from the corresponding compounds Ib1.01-Ib1.21 in that R16 is methyl: 
the compounds Ib3.01-Ib3.21, which differ from the corresponding compounds Ib1.01-Ib1.21 in that R16 and R17 are each methyl: 
the compounds Ib4.01-Ib4.21, which differ from the corresponding compounds Ib1.01-Ib1.21 in that R18 and R19 are each methyl: 
the compounds Ib5.01-Ib5.21, which differ from the corresponding compounds Ib1.01-Ib1.21 in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
the compounds Ib6.01-Ib6.21, which differ from the corresponding compounds Ib1.01 -Ib1.21 in that R14, R18 and R19 are each methyl and in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
the compounds Ib7.01-Ib7.21, which differ from the corresponding compounds Ib1.01-Ib1.21 in that R14, R15, R18 and R19 are each methyl and in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
Likewise, very particular preference is given to the compounds Ic1 ({circumflex over (=)}I where R2, R141 R15, R16, R17, R18 and R19=H and where the xe2x80x9cQxe2x80x94COxe2x80x94 fragmentxe2x80x9d is attached in position d, R1 is attached in position a and Z1 is attached in positions b and c) listed in Table 3 below:
Furthermore, very particular preference is given to the following hetaroyl derivatives of the formula I:
the compounds Ic2.01-Ic2.44, which differ from the compounds Ic1.01-Ic1.44 in that R16 is methyl: 
the compounds Ic3.01-Ic3.44, which differ from the compounds Ic1.01-Ic1.44 in that R16 and R17 are each methyl: 
the compounds Ic4.01-Ic4.44, which differ from the compounds Ic1.01-Ic1.44 in that R18 and R19 are each methyl: 
the compounds Ic5.01-Ic5.44, which differ from the corresponding compounds Ic1.01-Ic1.44 in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
the compounds Ic6.01-Ic6.44, which differ from the corresponding compounds Ic1.01-Ic1.44 in that R141 R18 and R19 are each methyl and in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
the compounds Ic7.01-Ic7.44, which differ from the corresponding compounds Ic1.01-Ic1.44 in that R14, R15, R18 and R19 are each methyl and in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
In addition very particular preference is given to the compounds Id1 ({circumflex over (=)}I where R2, R14, R15, R16, R17, R18 and R19=H and where the xe2x80x9cQxe2x80x94COxe2x80x94 fragmentxe2x80x9d is attached in position a, R1 is attached in position d and Z2 is attached in positions b and c) listed in Table 4 below:
Furthermore, very particular preference is given to the following hetaroyl derivatives of the formula I:
the compounds Id2.01-Id2.91, which differ from the compounds Id1.01-Id1.91 in that R16 is methyl: 
the compounds Id3.01-Id3.91, which differ from the compounds Id1.01-Id1.91 in that R16 and R17 are each methyl: 
the compounds Id4.01-Id4.91, which differ from the compounds Id1.01-Id1.91 in that R18 and R19 are each methyl: 
the compounds Id5.01-Id5.91, which differ from the corresponding compounds Id1.01-Id1.91 in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
the compounds Id6.01-Id6.91, which differ from the corresponding compounds Id1.01-Id1.91 in that R14, R18 and R19 are each methyl and in that the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
the compounds Id7.01-Id7.91, which differ from the corresponding compounds Id1.01-Id1.91 in that R14, R15, R18 and R19 are each methyl and the xe2x80x94CR16R17xe2x80x94 unit is replaced by Cxe2x95x90O: 
The hetaroyl derivatives of the formula I can be obtained by different routes, for example by the following process:
Reaction of cyclohexanediones of the formula II with an activated carboxylic acid IIIa or a carboxylic acid IIIb which is preferably activated in situ to give the acylation product, and subsequent rearrangement. 
L represents a nucleophilically replaceable leaving group, such as halogen, for example bromine or chlorine, heterocyclyl, for example imidazolyl or pyridyl, or carboxylate, for example acetate, trifluoroacetate, etc.
The activated hetaroylcarboxylic acid can be employed directly, as in the case of the hetaroyl halides, or formed in situ, for example by using dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic ester, 2-pyridine [sic] disulfite/triphenylphosphine, carbonyldiimidazole, etc.
It may be advantageous to carry out the acylation reaction in the presence of a base. It is advantageous to employ the reactants and the auxiliary base in equimolar amounts. In certain cases, a small excess of the auxiliary base, for example 1.2 to 1.5 molar equivalents based on II, may be advantageous.
Suitable auxiliary bases include tertiary alkylamines, pyridine and alkali metal carbonates. Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride and 1,2-dichloroethane, aromatic hydrocarbons, such as toluene, xylene and chlorobenzene, ethers,, such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, polar aprotic solvents, such as acetonitrile, dimethylformamide or dimethyl sulfoxide or esters, such as ethyl acetate, or mixtures thereof.
If carboxylic acid halides are employed as activated carboxylic acid component, it may be advantageous to cool the reaction mixture to 0-10xc2x0 C. when adding this reactant. Stirring is then continued at 20-100xc2x0 C., preferably at 25-50xc2x0 C., until the reaction has ended. Work-up is carried out in a conventional manner; for instance, the reaction mixture is poured into water and the product of value is extracted. Suitable solvents for this purpose are in particular methylene chloride, diethyl ether and ethyl acetate. After drying of the organic phase and removal of the solvent, the crude enol ester can be used for the rearrangement without any further purification.
The rearrangement of the enol esters to give the compounds of the formula I is advantageously carried out at from to 20-40xc2x0 C. in a solvent and in the presence of an auxiliary base using a cyano compound as catalyst.
Suitable solvents are, for example, acetonitrile, methylene chloride, 1,2-dichloroethane, ethyl acetate, toluene, or mixtures thereof. The preferred solvent is acetonitrile.
Suitable auxiliary bases are tertiary amines, such as triethylamine, pyridine or alkali metal carbonates, such as sodium carbonate and potassium carbonate, which are preferably employed in equimolar amounts or up to a fourfold excess, based on the enol ester. Preference is given to using triethylamine, preferably in double the equimolar amount based on the enol ester.
Suitable xe2x80x9crearrangement catalystsxe2x80x9d include inorganic cyanides, such as sodium cyanide and potassium cyanide, and organic cyano compounds, such as acetone cyanohydrin and trimethylsilyl cyanide. They are employed in an amount of from 1 to 50 mol percent, based on the enol ester. Preference is given to using acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of from to 15, preferably 10, mol percent based on the enol ester.
Work-up can be carried out in a known manner. The reaction mixture is acidified, for example with dilute mineral acid, such as 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, for example methylene chloride or ethyl acetate. The organic extract can be extracted with 5-10% strength alkali metal carbonate solution, for example with sodium carbonate solution or potassium carbonate solution. The aqueous phase is acidified and the resulting precipitate is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, dried and concentrated. (Examples of the preparation of enol esters of cyclohexane-1,3-diones and of the. cyanide-catalyzed rearrangement of the enol esters are described, for example, in EP-A 186 118 and U.S. Pat. No. 4 780 127).
Those cyclohexane-1,3-diones of the formula II used as starting materials which are not already known can be obtained in a conventional manner (for example EP-A 71 707, EP-A 142 741, EP-A 243 313, U.S. Pat. No. 4 249 937; WO 92/13821).
The carboxylic acid halides of the formula IIIa (where Lxe2x95x90Br, Cl) which are not already known can be obtained in a conventional manner by reacting the carboxylic acids of the formula IIIb with halogenating reagents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride and oxalyl bromide.
Those carboxylic acids of the formula IIIb which are not already known can be obtained in a conventional manner (The Chemistry of Heterocyclic Compounds, Vol. 32, xe2x80x9cQuinolines, Part I, II and IIIxe2x80x9d, Editor E. Taylor, publisher Wiley and Sons; The Chemistry of Heterocyclic Compounds, Vol. 38, xe2x80x9cIsoquinolines, Part I and IIxe2x80x9d, Editor A. Weissemberger and E. Taylor, publisher Wiley and Sons; T. Eicher, S. Hauptmann, xe2x80x9cChemie der Heterocyclenxe2x80x9d, Thieme Verlag 1994).
For example, unsubstituted or substituted aminobenzoic acids can be reacted with glycerol, unsubstituted or substituted glycerol derivatives or xcex1,xcex2-unsaturated carbonyl compounds by the method of Skraup to give the corresponding quinolinecarboxylic acids (cf. EP-A 294 685, DE-A 33 26 225) (Scheme 1) 
Likewise, it is possible to react unsubstituted or substituted anilines with glycerol, unsubstituted or substituted glycerol derivatives or xcex1,xcex2-unsaturated carbonyl compounds. After halogenation and exchange of the halogen function by cyanide (for example using copper(I) cyanide), the nitrile is hydrolyzed to give the corresponding quinolinecarboxylic acid (cf. Khim. Greterotsikl. Soedin 3 1980, 366 ({circumflex over (=)}CA 93, 71504)). (Scheme 2) 
Anilines which are not already known from the literature can be obtained by reducing the corresponding nitrobenzenes. Suitable for this purpose is for example catalytic hydrogenation, using, for example, Raney nickel, Pt/C, Pd/C or Rh/C, or reduction with iron powder, zinc powder, etc. in a mixture of organic acid, for example acetic acid or propionic acid, and a protic solvent, such as methanol, ethanol or water.
The nitrobenzenes can be synthesized by nitration, substitution reactions, etc. Scheme 3 exemplifies a synthetic sequence. 
Isoquinolinecarboxylic acids can be synthesized for example from halogenated isoquinolines by halogen/cyanide exchange (Chem. Ber. 52 (1919), 1749) and subsequent hydrolysis. (Scheme 4) 
It is also possible to prepare the corresponding aminoisoquinolines from nitrated isoquinolines by reduction (as mentioned above). Subsequent diazotization, Sandmeyer reaction with cyanide and hydrolysis afford isoquinolinecarboxylic acids (Scheme 5). 
Halogenated or nitrated isoquinolines can be prepared according to EP-A 633 262. Furthermore, it is possible to obtain halogenated isoquinolines starting from unsubstituted or substituted benzaldehydes by reaction with aminoacetaldehyde acetal and subsequent halogenation (Helv. Chim. Acta 68 (1985), 1828) (Scheme 6). 
The N-oxides of the quinoline- or isoquinolinecarboxylic acids can be obtained from the corresponding quinoline- or isoquinolinecarboxylic acids by oxidation with hydrogen peroxide. It may be advantageous to convert the corresponding acids first into the C1-C6-alkyl esters, to carry out the oxidation with hydrogen peroxide and then hydrolyze the ester.
2,3-Dihydroquinoline derivatives can be obtained, inter alia, by cyclization of xcex3-functionalized N-alkylanilines, with or without using Lewis acids or protic acids (Heterocycles 24 (1986), 2109; J. Am. Chem. Soc. 71 (1949), 1901).
Tetrahydroisoquinoline derivatives can be obtained from isoquinolines by reduction with hydrogen, if appropriate by metal catalysis, for example by Pt in acetic acid. However, it is also possible to react isoquinolines with dimethyl sulfate and to convert them into tetrahydroisoquinoline derivatives by reduction with sodium borohydride.